JP2007137042A - Polyvinyl alcohol-based film, polarizing film using same, and polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyvinyl alcohol-based film having a low birefringence and a polarizing film excellent in in-plane uniformity of polarization degree. <P>SOLUTION: The polyvinyl alcohol-based film has a width of not less than 3 m, wherein the in-plane retardation is not more than 30 nm and run-outs of the in-plane retardation in the film width direction are not more than 15 nm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyvinyl alcohol film. More specifically, the present invention relates to a polyvinyl alcohol film having a low birefringence, a method for producing the same, a polarizing film excellent in in-plane uniformity of polarization obtained from the film, and a polarizing plate.

  Conventionally, a polyvinyl alcohol-based film is prepared by dissolving a polyvinyl alcohol-based resin in a solvent such as water to prepare a stock solution, and then forming a film by a solution casting method (hereinafter referred to as a casting method), such as a metal heating roll. Is dried and heat-treated as necessary. The thus obtained polyvinyl alcohol-based film is used in many applications as a film excellent in transparency and dyeability, and one of its useful applications is a polarizing film. Such a polarizing film is used as a basic component of a liquid crystal display, and in recent years, its use has been expanded to display devices that require high quality and high reliability.

  Under such circumstances, with an increase in the size of a screen of a liquid crystal television or the like, there is a demand for a polarizing film that is more excellent in polarization performance, particularly in-plane uniformity of polarization performance than conventional products. In order to obtain a polarizing film with excellent in-plane uniformity of polarization performance, it is important that the polyvinyl alcohol film used as the original film of the polarizing film is optically homogeneous, especially the uniformity of the in-plane retardation value. It is. As such a countermeasure, for example, the difference in retardation value between two points separated by 1 cm in the width direction is 2 nm or less and the difference in retardation value between two points separated by 1 cm in the width direction is 5 nm or less. A polyvinyl alcohol polymer film having a thickness of 50 nm or less has been proposed (see, for example, Patent Document 1). In addition, it has been proposed to use a polyvinyl alcohol film in which the moisture content of the film when peeling from the casting substrate is set to less than 10% by weight (see, for example, Patent Document 2).

  In the following description, “retardation” means “in-plane retardation value” unless otherwise specified.

  However, even with these disclosed techniques, the retardation of the obtained polyvinyl alcohol film is not constant, and the polarization film produced using the polyvinyl alcohol film as a raw film has uneven polarization. . When the film width of the polyvinyl alcohol polymer film of Patent Document 1 is 2 m or more, there is a retardation difference of several tens of nm between two points on the film, and an optically uniform film having a width of 3 m or more is obtained. It cannot respond to the recent request. Furthermore, since the retardation itself is large, the optical design of the entire polarizing plate becomes complicated.

  In general, in the width direction, the polyvinyl alcohol-based film has a tendency that retardation at both ends increases and decreases at the center. One reason for this is that dehydration shrinkage occurs in the film drying process or heat treatment process, and stress is easily applied to both ends of the film. This stress is more likely to occur as the moisture content of the film becomes lower, and increases in a process where the moisture content becomes 20% by weight or less, particularly in a process where it becomes 10% by weight or less.

  In addition, as in Patent Document 2, when the moisture content of the film when peeling from the cast base material is less than 10% by weight, the retardation unevenness increases before the peeling step.

  The retardation unevenness in the width direction becomes more conspicuous as the film becomes wider. In the currently used 2 m wide polyvinyl alcohol film, there are about 10 nm retardation unevenness at both ends and the center. As the width of the film increases, it is more difficult to flatten the retardation in the width direction. This has been a factor in that an optically homogeneous film having a width of 3 m or more cannot be produced by the conventional production method.

JP 2002-28939 A JP-A-6-138319

  The present invention provides a polyvinyl alcohol film having a small in-plane retardation value and a small in-plane retardation value in the width direction, and an in-plane polarization degree corresponding to an increase in display area and resolution. An object of the present invention is to provide a polarizing film having excellent uniformity, and further a polarizing plate.

  The present invention relates to a polyvinyl alcohol film having a width of 3 m or more, a retardation value in the film plane of 30 nm or less, and a fluctuation of the retardation value in the film plane in the film width direction of 15 nm or less.

  It is preferable that the thickness of the film is 30 to 70 μm.

  The film is preferably used as a raw film for a polarizing film.

  In addition, the present invention includes a step of forming a film by a casting method, and a step of heat-treating the film with a plurality of hot rolls each having a surface temperature of 40 ° C. or higher, in the step of heat-treating The present invention relates to a method for producing a polyvinyl alcohol film, wherein the contact time between any one point in the film plane and each of the heat rolls is 1 to 6 seconds.

  In the manufacturing method, it is preferable that the total contact time between any one point in the film plane and each of the heat rolls is 30 to 100 seconds.

  In the said manufacturing method, it is preferable that the diameter of all the said heat rolls is 150-500 mm.

  The present invention also relates to a polarizing film comprising the polyvinyl alcohol film.

  Furthermore, the present invention relates to a polarizing plate comprising a protective film provided on at least one surface of the polarizing film.

  The polyvinyl alcohol film of the present invention has a low retardation value in the film plane and a small fluctuation of the retardation value in the film plane in the width direction. Therefore, when producing a polarizing film having excellent in-plane uniformity of polarization degree. Further, it is preferably used as a raw film.

  The present invention relates to a polyvinyl alcohol film having a retardation value in the film plane of 30 nm or less and a fluctuation of the retardation value in the film plane in the width direction of 15 nm or less in a polyvinyl alcohol film having a film width of 3 m or more. .

  In the present invention, “the retardation value in the film plane is N or less” means that the retardation value in the film plane is N or less at any location on the film plane. In addition, in this invention, evaluation of the retardation value in a film surface is made | formed by defining several measuring points in the width direction (TD) of the film made into a measuring object, and measuring the retardation value of each measuring point, respectively. . The retardation value is nx when the maximum refractive index in the film plane at each measurement point is nx, the refractive index in the film plane in the direction perpendicular to the direction of nx is ny, and the thickness of the film is d. -Ny) is a value defined by xd.

  In the present invention, “the fluctuation of the retardation value in the film plane in the film width direction” is the absolute value of the difference between the maximum value and the minimum value of the retardation value in the film width direction measured above. It is.

  The polyvinyl alcohol film of the present invention is produced from a polyvinyl alcohol resin by a production method described later. As the polyvinyl alcohol resin, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is usually used, but the polyvinyl alcohol film of the present invention is not necessarily limited to this. Instead, a resin obtained by saponifying a copolymer of vinyl acetate and a component copolymerizable with a small amount of vinyl acetate can also be used. Examples of components copolymerizable with vinyl acetate include unsaturated carboxylic acids (including salts, esters, amides, nitriles, etc.), olefins having 2 to 30 carbon atoms (ethylene, propylene, n-butene, isobutene, etc.). , Vinyl ethers, unsaturated sulfonates and the like.

  The weight average molecular weight of the polyvinyl alcohol resin of the present invention is not particularly limited, but the weight average molecular weight measured by gel permeation chromatography-low angle laser light scattering method (hereinafter referred to as GPC-LALLS method) is preferably 120,000 to 300,000. More preferably, it is 130000-26000, More preferably, it is 140000-200000. When the weight average molecular weight is less than 120,000, sufficient optical performance cannot be obtained when a polyvinyl alcohol-based resin is used as an optical film, and when it exceeds 300,000, stretching becomes difficult when the film is used as a polarizing film, and industrial production. Is difficult and undesirable.

  The saponification degree of the polyvinyl alcohol resin is preferably 97 to 100 mol%, more preferably 98 to 100 mol%, and still more preferably 99 to 100 mol%. When the saponification degree is less than 97 mol%, sufficient optical performance cannot be obtained when a polyvinyl alcohol-based resin is used as an optical film, which is not preferable.

  The retardation value in the film plane of the polyvinyl alcohol film of the present invention is 30 nm or less, preferably 5 to 30 nm, more preferably 5 to 25 nm, and still more preferably 5 to 20 nm. When a polyvinyl alcohol film is used as a raw film for a polarizing film, the retardation value greatly increases in the stretching step. Therefore, when the in-plane retardation value of the polyvinyl alcohol film that is the original film exceeds 30 nm, the influence of the retardation of the original film itself on the obtained polarizing film or polarizing plate is increased, and the optical properties of the liquid crystal cell are increased. The design becomes complicated. In addition, when the in-plane retardation value of the raw film is not controlled within a specific range, the retardation value of the polarizing film greatly varies from product to product, and a liquid crystal cell having stable quality can be manufactured. It becomes difficult. The retardation value in the film plane is preferably as small as possible. However, if the in-plane retardation value of the polyvinyl alcohol film, which is the raw film, is smaller than 5 nm, it is necessary to control the film forming conditions very strictly, and it is affected by a slight change in conditions. Tend to be inferior.

  Further, the fluctuation of the in-plane retardation value in the width direction of the polyvinyl alcohol film of the present invention is 15 nm or less, preferably 10 nm or less, more preferably 7 nm or less, and further preferably 5 nm or less. Moreover, the lower limit of the fluctuation of the in-plane retardation value in the film width direction is 0 (zero) as is clear from the above definition. When the fluctuation of the retardation value in the width direction exceeds 15 nm, when the film is used as the original film of the polarizing film, the deflection of the polarization degree of the obtained polarizing film is increased. Moreover, the smaller the fluctuation of the in-plane retardation value in the film width direction, the better.

  The width | variety of the polyvinyl alcohol-type film of this invention is 3 m or more, and it is preferable from the point of productivity at the time of polarizing film manufacture that it is 3.5 m or more. Moreover, since the upper limit of a film width | variety may be difficult to extend | stretch uniformly when uniaxially stretching when manufacturing a polarizing film, it is preferable that it is 6 m or less. Moreover, it is preferable that the thickness of the polyvinyl alcohol-type film of this invention is 30-100 micrometers, More preferably, it is 40-90 micrometers, Most preferably, it is 30-70 micrometers. If the thickness is less than 30 μm, stretching is difficult, and if it exceeds 100 μm, the film thickness accuracy is lowered, which is not preferable.

  The total light transmittance of the polyvinyl alcohol film of the present invention is preferably 90% or more, and more preferably 91% or more. The upper limit of the total light transmittance is 95%.

The tensile strength of polyvinyl alcohol film of the present invention is preferably 70N / mm ² or more, more preferably 75N / mm ² or more. The upper limit of the tensile strength is preferably 115N / mm ² or less, more preferably 110N / mm ^2. In addition, the tensile strength in the present invention is a tensile strength obtained by performing a tensile test at a tensile speed of 1000 mm / min on a test piece conditioned for 24 hours in an environment of 20 ° C. and 65% RH. .

  The complete dissolution temperature of the polyvinyl alcohol film of the present invention is preferably 65 ° C. or higher, more preferably 65 to 90 ° C., and more preferably 71 to 80 ° C. In the present invention, the complete dissolution temperature means that 2000 ml of water is put into a 2 L beaker, the temperature is raised to 30 ° C., a 2 cm × 2 cm film piece is added, and the water temperature is increased at a rate of 3 ° C./min while stirring. This is the temperature at which the film is completely dissolved. In addition, the thickness of a film piece will not be specifically limited if it is 30-70 micrometers.

  In general, for a polyvinyl alcohol film, a polyvinyl alcohol resin aqueous solution is prepared using the polyvinyl alcohol resin as described above, and the aqueous solution is cast on a drum-type roll to form a film, dry, and heat-treat as necessary. It is manufactured by. The polyvinyl alcohol film of the present invention can be produced, for example, by a production method described later.

  Below, the manufacturing method of the polyvinyl alcohol-type film of this invention is demonstrated.

  The method for producing a polyvinyl alcohol film of the present invention includes a step of forming a film by a casting method, and a step of heat-treating the film after film formation with a plurality of hot rolls each having a surface temperature of 40 ° C. or more. In the process of including and heat-treating, the contact time between any one point in the film plane and each heat roll is 1 to 6 seconds.

  In addition, said "heat-processing process" includes both the process of drying a film, and the heat processing process given with respect to the film after drying.

  In the method for producing a polyvinyl alcohol film of the present invention, first, an aqueous polyvinyl alcohol resin solution containing the polyvinyl alcohol resin as described above is prepared. The concentration of the aqueous polyvinyl alcohol resin solution is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, and particularly preferably 20 to 30% by weight. If the concentration is less than 10% by weight, the drying load becomes large and the production capacity is inferior. If the concentration exceeds 50% by weight, the viscosity becomes too high and uniform dissolution cannot be achieved.

  Moreover, in the polyvinyl alcohol-based resin aqueous solution, as needed, generally used plasticizers such as glycerin, diglycerin, triglycerin, ethylene glycol, triethylene glycol, polyethylene glycol, nonionic, anionic, A cationic surfactant may be added.

  When preparing the polyvinyl alcohol-based resin aqueous solution, the temperature condition for dissolving the resin is preferably 50 to 200 ° C, more preferably 100 to 150 ° C. If it is less than 50 degreeC, the load of a motor will become large, and when it exceeds 200 degreeC, since degradation of polyvinyl alcohol-type resin will arise, it is unpreferable. The time for dissolving the resin is preferably 1 to 20 hours, more preferably 2 to 10 hours. If it is less than 1 hour, dissolution is insufficient, and if it exceeds 20 hours, productivity is inferior, which is not preferable.

  Next, the obtained polyvinyl alcohol-based resin aqueous solution is usually defoamed. Examples of the defoaming method include stationary defoaming and defoaming with a multi-screw extruder. In the production method of the present invention, a method of defoaming with a multi-screw extruder is preferable. The multi-screw extruder is not particularly limited as long as it is a multi-screw extruder having a vent. Usually, a twin-screw extruder having a vent is used.

In the defoaming process using a multi-screw extruder, a polyvinyl alcohol-based resin aqueous solution is supplied to the multi-screw extruder, and the resin temperature of the vent portion is preferably 100 to 200 ° C., more preferably 110 to 150 ° C. It is carried out under conditions where the machine tip pressure is preferably ^{2 to} 100 kg / cm ² , more preferably 5 to 70 kg / cm ² . If the resin temperature of the vent portion is less than 100 ° C., defoaming becomes insufficient, and if it exceeds 200 ° C., resin degradation occurs. Further, when the pressure at the extruder tip is less than 2 kg / cm ² , defoaming is insufficient, and when it exceeds 100 kg / cm ² , resin leakage or the like occurs in the piping, and stable production cannot be achieved.

  After the defoaming treatment, the polyvinyl alcohol-based resin aqueous solution discharged from the multi-screw extruder is introduced into the T-type slit die by a certain amount. Thereafter, the aqueous polyvinyl alcohol resin solution discharged from the slit die is cast to form a film.

  As the T-type slit die, a T-type slit die having an elongated rectangle is usually used.

  Moreover, it is preferable that the resin temperature of a T-type slit die exit is 80-100 degreeC, More preferably, it is 85-98 degreeC. If the resin temperature at the exit of the T-shaped slit die is less than 80 ° C., flow failure occurs, and if it exceeds 100 ° C., foaming is not preferable.

  In casting a polyvinyl alcohol-based resin aqueous solution, a drum-type roll or an endless belt is generally used, but it is preferable to use a drum-type roll from the viewpoints of widening, lengthening, and film thickness uniformity.

  In casting a film with a drum-type roll, for example, the rotation speed of the drum-type roll is preferably 5 to 30 m / min, and particularly preferably 6 to 20 m / min. The surface temperature of the drum roll is preferably 70 to 99 ° C, more preferably 75 to 97 ° C. If the surface temperature of the drum-type roll is less than 70 ° C., drying is poor, and if it exceeds 99 ° C., the film is foamed, which is not preferable. The size of the drum-type roll is not particularly limited as long as a film having a width of 3 m or more is formed. For example, the diameter of the roll is preferably 3100 to 5000 mm, more preferably 3100 to 4000 mm.

  The moisture content of the film cast by a drum-type roll is preferably 10 to 30% by weight, particularly preferably 15 to 25% by weight. If it exceeds 30% by weight, peeling from the roll is difficult, and the load of the drying process increases, which is not preferable. On the other hand, if it is less than 10% by weight, retardation is increased by rapid water evaporation, which is not preferable.

  The film after film formation obtained by the method described above is dried while its front and back surfaces are alternately brought into contact with a plurality of hot rolls, and then heat-treated as necessary. In the present invention, the heat roll is a roll used in a step after the step of casting a film using a drum roll by a casting method, has a heating device, and the surface temperature of the roll is 40 ° C. It means the roll which is the above. When the surface temperature of the roll is less than 40 ° C., the drying efficiency is poor and the meaning of the hot roll is poor. A roll that does not have a heating device and is merely intended for conveying a film does not correspond to the heat roll of the present invention even if its surface temperature exceeds 40 ° C. The contact length between the film and the heat roll in the circumferential direction of the heat roll (hereinafter referred to as the contact length in the circumferential direction) is preferably ¼ or more of the circumference. When the contact length is less than 1/4 of the circumference, the drying efficiency is poor and the meaning of the hot roll is poor.

  Usually, in the drying process or heat treatment process of a polyvinyl alcohol film, the film shrinks due to dehydration. When a film is heated using a hot roll, a complex shrinkage stress acts in both the flow direction and the width direction during the contact between the film and the roll, and this stress causes retardation. Further, the longer the contact time between the film per roll and the roll, the greater the retardation value and unevenness. In particular, the contact length between the film and the heat roll in the width direction of the roll (hereinafter referred to as the contact length in the width direction) tends to cause retardation unevenness because of its large value, and the retardation is large at both ends where the stress increases. , Tend to be lower in the center. The contact in this case does not necessarily mean complete adhesion between the roll and the film, and includes a case where a slight gap (air layer) exists.

  In order to avoid such a problem of retardation unevenness, it is necessary to reduce the contact time between the film per roll and the roll in the drying process or the heat treatment process. The contact length itself is not a problem. Retardation does not occur if the film passes in a short time even if the contact length is long. Conversely, if the film is heated on a roll for a long time even if the contact length is short, the retardation increases. Therefore, the main point of the method for producing the polyvinyl alcohol film of the present invention is to eliminate the time for generating the stress.

  Specific methods for reducing the time for generating stress include reducing the diameter of individual heat rolls and improving the conveyance speed. When the amount of heat applied to the film is constant throughout the manufacturing process, reducing the diameter of the heat roll means increasing the number of heat rolls as a whole line. This makes it possible to predict a decrease in productivity, but the productivity can be maintained by improving the conveyance speed. Moreover, since stress relaxation between frequent hot rolls is possible, a film having no retardation unevenness can be obtained with a high yield.

  That is, in the method for producing a polyvinyl alcohol film of the present invention, the contact time between each heat roll and any one point in the film plane in the step of heat-treating the film is 1 to 6 seconds. The contact time is preferably 1 to 5.5 seconds, more preferably 2 to 5 seconds, and particularly preferably 2 to 4.5 seconds. If the contact time is less than 1 second, drying tends to be insufficient, and if it exceeds 6 seconds, retardation in the width direction of the film increases. In addition, this contact time is controllable by adjusting the roll diameter of a heat roll, and the conveyance speed of a film.

  The total contact time between each heat roll and any one point in the film plane is preferably 30 to 100 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 80 seconds. If it exceeds 100 seconds, the retardation of the film increases, which is not preferable. If it is less than 30 seconds, drying is insufficient, which is not preferable.

  As a matter of course, the contact time depends on the conveyance speed of the film. The conveyance speed of the film is preferably 4 to 15 m / min, more preferably 8 to 14 m / min, and particularly preferably 9 to 13 m / min. If it is less than 4 m / min, the productivity is poor, and if it exceeds 15 m / min, drying tends to be insufficient, which is not preferable.

  10-40 are preferable, and, as for the total number of the heat roll used for the process of heat-processing a film, More preferably, it is 12-30, Especially preferably, it is 13-25. If it is less than 10, drying becomes insufficient, and if it exceeds 40, the equipment load increases, which is not preferable.

  The diameter of the heat roll is preferably 150 to 500 mm (outer circumference 471 to 1570 mm), more preferably 200 to 450 mm (outer circumference 628 to 1413 mm), and further preferably 250 to 400 mm (outer circumference 785 to 1256 mm). If the diameter exceeds 500 mm, the retardation tends to increase, which is not preferable. If the diameter is less than 150 mm, the contact area with the film is insufficient and the drying efficiency tends to be inferior. Moreover, it is preferable that all the heat rolls have a diameter within the above range.

  Moreover, the contact length of the circumferential direction of a film and each heat roll becomes like this. Preferably it is 200-1400 mm, More preferably, it is 300-1300 mm, More preferably, it is 400-1200 mm.

  Although the width | variety of a heat roll will not be specifically limited if a process can be performed to a 3 m wide film, Preferably it is 3100-5000 mm, More preferably, it is 3200-4500, Most preferably, it is 3300-4200 mm.

  Moreover, it is preferable that the distance between each heat roll shall be 0.5-10 mm, Furthermore, 0.5-5 mm. However, in this case, it is not necessary to make all the distances between the heat rolls the same, and the distances between the heat rolls may be different.

  The surface temperature of a hot roll is 40 degreeC or more, Preferably it is 40-150 degreeC, More preferably, it is 50-120 degreeC, Most preferably, it is 60-110 degreeC. If the surface temperature is less than 40 ° C., the drying ability is poor, and if it exceeds 150 ° C., an appearance defect is caused, which is not preferable. The surface temperature of the heat roll does not need to be constant, and may be, for example, high in the early stage of drying with a high water content and low in the later stage. Further, the heat treatment performed for the purpose of crystallization may be performed by gradually using a hot roll or by gradually using a low-temperature roll. Moreover, you may perform the heat processing by the floating method which heats a film with a warm air from both surfaces after drying and heat processing with a hot roll. In this case, the heat treatment temperature is suitably 50 to 150 ° C., and the heat treatment time is suitably 10 to 120 seconds.

  The draw ratio of the hot roll is preferably 0.9 to 1.1, more preferably 0.95 to 1.07, and still more preferably 0.98 to 1.05. If it is less than 0.9, the film will be loosened during conveyance, and if it exceeds 1.1, the retardation increases due to tensile stress, which is not preferable.

  In addition, in this invention, a draw ratio is a numerical value calculated | required by the rotational speed of a heat roll (back | latter stage) / rotation speed of a heat | fever roll (front stage).

  It is preferable that the moisture content of the film after the heat treatment, that is, after drying (after heat treatment when heat treatment is performed) is 5% by weight or less. More preferably, it is 1-4 weight%, More preferably, it is 2-3 weight%. When it exceeds 5% by weight, poor appearance tends to occur during storage of the film.

  In the method for producing a polyvinyl alcohol film of the present invention, by specifying the contact time between the film and the heat roll in the step of heat-treating the film, the retardation value in the film plane in the width direction is low, particularly in the width direction. A polyvinyl alcohol-based film with a small amount can be obtained.

  The polyvinyl alcohol film of the present invention has a small retardation value in the film plane and a small fluctuation of the retardation value in the film plane in the width direction. Therefore, when producing a polarizing film having excellent in-plane uniformity of polarization degree. Further, it is preferably used as a raw film.

  Hereinafter, the manufacturing method of the polarizing film of this invention using the polyvinyl alcohol-type film of this invention is demonstrated.

  The polarizing film of the present invention is produced through processes such as normal dyeing, stretching, boric acid crosslinking and heat treatment. As a method for producing a polarizing film, a polyvinyl alcohol film is stretched and immersed in an iodine or dichroic dye solution and dyed, and then treated with a boron compound. After stretching and dyeing are performed simultaneously, the boron compound is treated. There are a method, a method of dyeing with iodine or a dichroic dye and stretching, and then a method of treating with a boron compound, a method of dyeing and then stretching in a solution of a boron compound, etc., which can be appropriately selected and used. As described above, the polyvinyl alcohol film (unstretched film) may be stretched and dyed and further subjected to boron compound treatment separately or simultaneously, but during at least one of the dyeing step and the boron compound treatment step. It is desirable from the viewpoint of productivity to carry out uniaxial stretching.

  Stretching is preferably performed 3 to 10 times, preferably 3.5 to 6 times in a uniaxial direction. At this time, the film may be slightly stretched in the direction perpendicular to the stretching direction (stretching to prevent shrinkage in the width direction or more). The temperature condition during stretching is desirably selected from 40 to 170 ° C. Furthermore, the draw ratio may be finally set within the above range, and the drawing operation may be performed not only in one stage but also in any stage of the manufacturing process.

  The polyvinyl alcohol film is dyed by bringing the film into contact with a liquid containing iodine or a dichroic dye. Usually, an iodine-potassium iodide aqueous solution is used, the iodine concentration is 0.1 to 2 g / L, the potassium iodide concentration is 10 to 50 g / L, and the potassium iodide / iodine weight ratio is 20 to 100. It is preferable that The dyeing time is practically about 30 to 500 seconds, and the temperature of the treatment bath is preferably 5 to 50 ° C. In addition to the water solvent, a small amount of an organic solvent compatible with water may be contained. Any means such as dipping, coating, spraying, etc. can be applied as the contact means.

  The dyed film is generally then treated with a boron compound. As the boron compound, boric acid and borax are practical. The boron compound is preferably used at a concentration of about 0.5 to 2 mol / L in the form of an aqueous solution or a water-organic solvent mixture, and it is practically desirable that a small amount of potassium iodide coexists in the solution. The treatment method is preferably an immersion method, but of course, an application method and a spray method can also be carried out. The temperature during the treatment is preferably about 50 to 70 ° C., the treatment time is preferably about 5 to 20 minutes, and if necessary, the stretching operation may be performed during the treatment.

  The polarizing film of the present invention thus obtained can be used as a polarizing plate by laminating and bonding an optically isotropic polymer film or sheet as a protective film on one or both surfaces thereof. Examples of the protective film include films of cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, polystyrene, polyethersulfone, polyarylene ester, poly-4-methylpentene, polyphenylene oxide, cyclo-based or norbornene-based polyolefin. Or a sheet | seat is mentioned.

  In addition, for the purpose of reducing the thickness of the polarizing film of the present invention, instead of the protective film, a curable resin such as a urethane resin, an acrylic resin, or a urea resin is applied and laminated on one or both surfaces. You can also

  The polarizing film of the present invention (or at least one surface thereof laminated with a protective film or a curable resin) is a method in which a transparent pressure-sensitive adhesive layer is usually known on one surface as necessary. In some cases, it is formed and put into practical use. Examples of pressure-sensitive adhesive layers include acrylic acid esters such as butyl acrylate, ethyl acrylate, methyl acrylate, and 2-ethylhexyl acrylate, and acrylic acid, maleic acid, itaconic acid, methacrylic acid, crotonic acid, and the like. Copolymers with α-monoolefin carboxylic acids (including those added with vinyl monomers such as acrylonitrile, vinyl acetate, and styrene) may interfere with the polarization characteristics of the polarizing film. However, the present invention is not limited to these, and any pressure-sensitive adhesive having transparency can be used. For example, a polyvinyl ether type or a rubber type may be used.

  The polarization degree of the polarizing film of the present invention is preferably 99.5% or more, more preferably 99.8% or more. If the degree of polarization is less than 99.5%, the contrast in the liquid crystal display tends not to be secured. The upper limit of the degree of polarization of the polarizing film is 100%.

The degree of polarization is the light transmittance (H ₁₁ ) measured at the wavelength λ with the two polarizing films overlapped so that the orientation directions thereof are the same direction, and the two polarizing films, It is calculated according to the following equation from the light transmittance (H ₁ ) measured at the wavelength λ in a state where the alignment directions are perpendicular to each other.
[(H ₁₁ −H ₁ ) / (H ₁₁ + H ₁ )] ^1/2

  Further, the deflection of the polarization degree in the width direction of the polarizing film of the present invention is preferably 0.5% or less, more preferably 0.3% or less. If the deflection of the polarization degree exceeds 0.5%, color unevenness tends to occur in the liquid crystal display.

  In the present invention, the “polarization degree fluctuation” is a value defined as a difference (absolute value) between the maximum value and the minimum value of the polarization degree when the polarization degree is measured over the entire width in the width direction of the polarizing film. is there.

  The single transmittance of the polarizing film of the present invention is preferably 43% or more. Particularly preferably, it is 44% or more. If it is less than 43%, it tends to be impossible to achieve high brightness of the liquid crystal display. The upper limit of the single transmittance of the polarizing film is 46%.

  The polarizing film of the present invention includes an electronic desk calculator, an electronic watch, a word processor, a personal computer, a portable information terminal, a liquid crystal display device such as an instrument for automobiles and machinery, sunglasses, eye protection glasses, stereoscopic glasses, a display element (CRT, Used for reflection-reducing layers for LCD, etc., medical equipment, building materials, toys and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples, unless the summary is exceeded. In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

(1) Weight average molecular weight It measures on condition of the following by GPC-LALLS method.
1) GPC
Apparatus: Waters type 244 gel permeation chromatograph column: Tosoh Corporation TSK-gel-GMPW _XL (inner diameter 8 mm, length 30 cm, 2 pieces)
Solvent: 0.1 M Tris buffer (pH 7.9)
Flow rate: 0.5 ml / min Temperature: 23 ° C
Sample concentration: 0.040%
Filtration: 0.45 μm Mysori Disc W-25-5 manufactured by Tosoh Corporation
Injection volume: 0.2ml
Detection sensitivity (differential refractive index detector): 4 times

2) LALLS
Apparatus: Chromatrix KMX-6 type low angle laser light scattering photometer Temperature: 23 ° C
Wavelength: 633nm
Second virial coefficient × concentration: 0 mol / g
Refractive index density change (dn / dc): 0.159 ml / g
Filter: MILLIPORE 0.45 μm filter HAWP01300
Gain: 800mV

(2) In-plane retardation value The obtained film is cut into a width (TD length) of 3000 mm × a length (MD length) of 50 mm to prepare a strip sample. About the obtained sample, using KOBRA-21SDH (manufactured by Oji Scientific Instruments Co., Ltd.), measuring points are defined at regular intervals of 10 mm in the width direction over the entire width, and the in-plane retardation value at each measuring point is determined. taking measurement. Table 2 shows the obtained retardation value range, average value, and absolute value of the difference between the maximum value and the minimum value as the fluctuation of the retardation value.

(3) Polarization degree The obtained polarizing film is cut into a width (TD length) of 1000 mm × a length (MD length) of 50 mm to prepare a strip sample. About the obtained sample, a high-speed multiwavelength birefringence measuring apparatus (Otsuka Electronics Co., Ltd. product: RETS-2000 wavelength: 550 nm) is used to measure the degree of polarization over the entire width at a pitch of 10 mm in the width direction. Table 2 shows the obtained range of polarization degree, the average value, and the absolute value of the difference between the maximum value and the minimum value as deflection of the polarization degree.

Example 1
(Manufacture of polyvinyl alcohol film)
A 200 l tank is charged with 40 kg of a polyvinyl alcohol resin having a weight average molecular weight of 142,000 and a saponification degree of 99.8 mol%, water of 100 kg, a plasticizer of 4.2 kg, and a release agent of polyoxyethylene dodecylamine of 42 g and stirring. While raising the temperature to 150 ° C., a uniformly dissolved polyvinyl alcohol resin aqueous solution having a resin concentration of 25% was obtained. Next, the polyvinyl alcohol-based resin aqueous solution was supplied to a twin-screw extruder and defoamed, and then cast from a T-type slit die onto a drum-type roll to form a film. The conditions for such casting film formation were as follows.

Drum type roll Diameter: 3 m, width: 3.3 m, rotation speed: 10 m / min, surface temperature: 90 ° C., resin temperature at T-type slit die outlet: 95 ° C.
The moisture content of the film obtained after film formation was 23%. And it dried, making the surface and back surface of this film contact a heat roll alternately on condition of the following.

Heat roll (drying roll)
Diameter: 350 mm, Width: 3.3 m, Number: 18, Rotational speed: 10 m / min, Surface temperature: 80 ° C., Contact length in the circumferential direction of the film and each roll: 550 mm (contact time: 3.3 seconds)
The total contact time between the film and the hot roll was 59 seconds. Thereafter, further heat treatment (condition: floating dryer (120 ° C., length 6 m)) was performed. The water content of the film after the heat treatment was 4%. Table 2 shows retardation values of the obtained polyvinyl alcohol film (width 3 m, thickness 50 μm). In addition, the minimum value of retardation was a film center part, and the maximum value was the both ends.

(Manufacture of polarizing film)
The obtained polyvinyl alcohol film was immersed in an aqueous solution consisting of 0.2 g / L of iodine and 15 g / L of potassium iodide for 240 seconds at 30 ° C., and then 60 g / L of boric acid and 30 g / L of potassium iodide. While being immersed in an aqueous solution (55 ° C.) of the composition, boric acid treatment was performed for 5 minutes while simultaneously uniaxially stretching four times. Then, it dried and obtained the polarizing film. Table 2 shows the degree of polarization of the obtained polarizing film.

Examples 2-6, Comparative Examples 1-2
A polyvinyl alcohol-based film and a polarizing film were obtained in the same manner as in Example 1 except for the conditions in Table 1. The performances of the obtained polyvinyl alcohol film and polarizing film were as shown in Table 2.

  According to the present invention, a polyvinyl alcohol film having a small retardation value in the film plane and a small fluctuation of the retardation value in the film plane in the width direction can be obtained. Moreover, since the polyvinyl alcohol-type film of this invention is excellent in optical homogeneity, it can be used as a raw film at the time of manufacturing the polarizing film excellent in the in-plane uniformity of the polarization degree.

Claims (11)

The width is 3 m or more,
The retardation value in the film plane is 30 nm or less, and
A polyvinyl alcohol-based film characterized in that the fluctuation of the retardation value in the film plane in the film width direction is 15 nm or less. The polyvinyl alcohol film according to claim 1, wherein the film has a thickness of 30 to 70 μm. 3. The polyvinyl alcohol film according to claim 1, wherein the polyvinyl alcohol film is used as an original film of a polarizing film. A step of forming a film by a casting method; and
Heat-treating the film with a plurality of hot rolls each having a surface temperature of 40 ° C. or higher,
The method for producing a polyvinyl alcohol film, wherein a contact time between any one point in the film surface and each of the heat rolls in the heat treatment step is 1 to 6 seconds. The method for producing a polyvinyl alcohol film according to claim 4, wherein the total contact time between any one point in the film plane and each of the heat rolls is 30 to 100 seconds. The diameter of all the said heat rolls is 150-500 mm, The manufacturing method of the polyvinyl alcohol-type film of Claim 4 or 5 characterized by the above-mentioned. A step of forming a film by a casting method; and
Including the step of heat-treating the film with a plurality of hot rolls each having a surface temperature of 40 ° C. or higher,
The polyvinyl alcohol according to any one of claims 1 to 3, wherein a contact time between any one point in the film surface and each of the heat rolls in the heat treatment step is 1 to 6 seconds. -Based film manufacturing method. The method for producing a polyvinyl alcohol film according to claim 7, wherein the total contact time between any one point in the film plane and each of the heat rolls is 30 to 100 seconds. The diameter of all the said heat rolls is 150-500 mm, The manufacturing method of the polyvinyl alcohol-type film of Claim 7 or 8 characterized by the above-mentioned. A polarizing film comprising the polyvinyl alcohol-based film according to claim 1. A polarizing plate comprising a protective film on at least one surface of the polarizing film according to claim 10.